Академический Документы
Профессиональный Документы
Культура Документы
Potentiometry,
Voltammetry,
Amperometry,
Applications
Study Redox Chemistry
electron transfer reactions, oxidation, reduction,
organics & inorganics, proteins
Adsorption of species at interfaces
Electrochemical analysis
Measure the Potential of reaction or process
E = const + k log C (potentiometry)
Measure the Rate of a redox reaction; Current (I)
= k C (voltammetry)
Electrochemical Synthesis
Organics, inorganics, materials, polymers
Electrochemical Cells
Galvanic Cells and Electrolytic Cells
Galvanic Cells power output; batteries
Potentiometric cells (I=0) read Chapter 2
measure potential for analyte to react
current = 0 (reaction is not allowed to occur)
Equil. Voltage is measured (Eeq)
O + ne = R,
Eo in Volts
Typical 3-electrode
Voltammetry cell
Reference electrode
Counter
electrode
Working electrode
O
e-
O
Mass transport
R
End of Working electrode
R
Bulk solution
Reduction at electrode
Causes current flow in
External circuit
Voltammetry
Quiet or stirred solution
Vary (scan) Eapplied
Measure Current
Indicates reaction rate
Reaction at electrode surface produces concentration gradient with
bulk solution
Mass transport brings unreacted species to electrode surface
electrode
material
reference
N2
inlet
counter
working electrode
Electrochemical cell
E, V
time
reduction
Polarization - theoretical
Ideally Polarized Electrode
reduction
No oxidation or reduction
oxidation
Overvoltage or Overpotential
= E Eeq; can be zero or finite
E < Eeq < 0
Amt. of potential in excess of Eeq needed to
make
a non-reversible reaction happen, for example
reduction
Ee
q
a = activity
Voltammetric Methods
Voltammetry are based on measurement of current as a function of the potential
applied to a small electrode. Unlike potentiometry measurements, which employ
only two electrodes, voltammetric measurements utilize a three electrode
electrochemical cell. The use of the three electrodes (working, auxiliary, and
reference) along with the potentiostat instrument allow accurate application of
potential functions and the measurement of the resultant current.
A Three electrode cell used
for anodic stripping
voltammetry.
The working electrode is a
glassy carbon electrode on
which a thin mercury film has
been deposited.
An electrolysis step is used to
deposit lead into the mercury
film as an amalgam.
After the electrolysis step, the
potential is scanned
anodically toward positive
values to oxidize (strip) the
metal from the film.
CYCLIC VOLTAMMETRY
- Involves linear scanning of potential of a stationary
electrode using a triangular waveform
- Solution is unstirred
- The most widely used technique for quantitative analysis
of redox reactions
Provides information on
- the thermodynamics of redox processes
- the kinetics of heterogeneous electron transfer reactions
- the kinetics of coupled reactions
CYCLIC VOLTAMMETRY
Voltammogram
Linear sweep voltammogram for the reduction of a hypothetical species A to give a
product P. The limiting current il is proportional to the analyte concentration and is
used for quantitative analysis. The half-wave potential E1/2 is related to the standard
potential for the half reaction and is often used for qualitative identification of species.
A + ne
iI = kCA
Cyclic Voltammetry
t0 t1 : cathodic wave
Instead of leaving off at the top of the
wave, current decreases at more
negative potential
diffusion is too slow to replenish
analyte near the electrode
t1 t2 : anodic wave
The potential is reversed and, reduced
product near the electrode is oxidized
Epa Epc
2.22 RT 57.0
(mV)
nF
n
(at 25 oC)
Fe(C5H5)2
CYCLIC VOLTAMMETRY
- Assume only O is present initially
- A negative potential sweep results in the reduction of O to R
(starting from a value where no reduction of O initially occurs)
- As potential approaches Eo for the redox process, a cathodic
current is observed until a peak is reached
- The direction of potential sweep is reversed after going
beyond the region where reduction is observed
- This region is at least 90/n mV beyond the peak
CYCLIC VOLTAMMETRY
- R molecules generated and near the electrode surface
are reoxidized to O during the reverse (positive) scan
- Results in an anodic peak current
- The characteristic peak is a result of the formation of a
diffusion layer near the electrode surface
- The forward and reverse currents have the same shape
CYCLIC VOLTAMMETRY
- Increase in peak current corresponds to achievement
of diffusion control
- Decrease in current (beyond the peak) does not depend
on the applied potential but on t-1/2
Characteristic Parameters
- Anodic peak current (ipa)
- Cathodic peak current (ipc)
- Anodic peak potential (Epa)
- Cathodic peak potential (Epc)
CYCLIC VOLTAMMETRY
Reversible Systems
- Peak current for a reversible couple is given by the
Randles-Sevcik equation (at 25 oC)
CYCLIC VOLTAMMETRY
Reversible Systems
ip is proportional to C
ip is proportional to 1/2
- Implies electrode reaction is controlled by mass transport
ipa/ipc 1 for simple reversible couple
- For a redox couple
E
o
E pa E pc
2
CYCLIC VOLTAMMETRY
Reversible Systems
- The separation between peak potentials
E p E pa E pc
0.059
V
n
CYCLIC VOLTAMMETRY
Reversible Systems
- The half peak potential
E p/2
0.028
E 1/2
V
n
CYCLIC VOLTAMMETRY
Irreversible Systems
- Systems with sluggish electron transfer
- Individual peaks are reduced in size and are widely separated
- Characterized by shift of the peak potential with scan rate
o
RT
k
n a F
o
Ep E
0.78 ln 1/2 ln
n a F
D
RT
i p 2.99 x 10
1/2
1/2
n n a ACD1/2 1/2
CYCLIC VOLTAMMETRY
Irreversible Systems
= transfer coefficient
na = number of electrons involved in a charge transfer step
ko = standard heterogeneous rate constant (cm/s)
- ip is proportional to C but lower depending on the value of
For = 0.5
ip,reversible/ip,irreversible = 1.27
- That is irreversible peak current is ~ 80% of reversible ip
CYCLIC VOLTAMMETRY
Quasi-reversible Systems
- Current is controlled by both charge transfer and mass transport
- Voltammograms are more drawn out
- Exhibit larger separation in peak potentials compared
to reversible systems
- Shape depends on heterogeneous rate constant and scan rate
- Exhibits irreversible behavior at very fast scan rates
CYCLIC VOLTAMMETRY
Applications
1. Study of Reaction Mechanisms
E = redox step and C = chemical step
E
- Only redox step
O + ne- R
CYCLIC VOLTAMMETRY
Applications
E = redox step and C = chemical step
EC
- Redox step followed by chemical step
O + ne- R + A Z
- R reacts chemically to produce Z
- Z is electroinactive
- Reverse peak is smaller since R is chemically removed
ipa/ipc < 1
- All of R can be converted to Z for very fast chemical reactions
CYCLIC VOLTAMMETRY
Applications
E = redox step and C = chemical step
EC
- Redox step followed by chemical step
O + ne- R + A Z
Examples
- Ligand exchange reactions as in iron porphyrin complexes
- Oxidation of chlorpromazine to produce a radical cation and
subsequent reaction with water to produce sulfoxide
CYCLIC VOLTAMMETRY
Applications
E = redox step and C = chemical step
EC
- Catalytic regeneration of O during a chemical step
O + ne- R + A O
- Peak ratio is unity
Example
- Oxidation of dopamine in the presence of ascorbic acid
CYCLIC VOLTAMMETRY
Applications
E = redox step and C = chemical step
CE
- Slow chemical reaction precedes the electron transfer step
Z O + ne- R
ipa/ipc > 1 (approaches 1 as scan rate decreases)
ipa is affected by the chemical step
ipc is not proportional to 1/2
CYCLIC VOLTAMMETRY
Applications
E = redox step and C = chemical step
ECE
- Chemical step interposed between redox steps
O1 + ne- R1 O2 + ne- R2
- The two redox couples are observed separately
- The system behaves as EE mechanism for very fast
chemical reactions
- Electrochemical oxidation of aniline
CYCLIC VOLTAMMETRY
Applications
2. Study of Adsorption Processes
- For studying the interfacial behavior of electroactive compounds
Symmetric CV
Ep = 0
- Observed for surface-confined nonreacting species
- Ideal Nernstian behavior
CYCLIC VOLTAMMETRY
Applications
Symmetric CV
- Peak current is directly proportional to surface coverage ()
and scan rate ()
n 2 F 2 A
ip
4RT
Holds for relatively
- slow scan rates
- slow electron transfer
- no intermolecular attractions within the adsorbed layer
CYCLIC VOLTAMMETRY
Applications
Symmetric CV
Q (area under peak)
Q nFA
current
Ep,1/2
volts
CYCLIC VOLTAMMETRY
Applications
Symmetric CV
- The surface coverage can be determined from the
area under the peak (Q)
Q = quantity of charge consumed
Q nFA
or
nFA
CYCLIC VOLTAMMETRY
Applications
3. Quantitative Determination
- Based on the measurement of peak current
Additional methods
SPECTROELECTROCHEMISTRY
- Simultaneous measurement of spectral and electrochemical signals
- Coupling of optical and electrochemical methods
- Employs optically transparent electrode (OTE) that allows light to
pass through the surface and adjacent solution
Examples
Indium tin oxide (ITO), platinum, gold, silver, nickel
deposited on optically transparent glass or quartz substrate
SPECTROELECTROCHEMISTRY
-2.5
Epc
Current (Milliamps)
-1.5
ipc
-0.5
0.5
ipa
1.5
Epa
2.5
0.8
0.6
0.4
0.2
Volts vs Ag/AgCl
-0.2
-0.4
Modulated Absorbance
Am = -log(I/Io)
SPECTROELECTROCHEMISTRY
Applications
- Useful for elucidation of reaction kinetics and mechanisms
(for probing adsorption and desorption processes)
- Thin layer SE methods for measuring Eo and n (Nernst equation)
- Infrared SE methods for providing structural information
- UV-Vis spectroscopic procedures
- Vibration spectroscopic investigations
- Luminescence reflectance and scattering studies
ELECTROCHEMILUMINESCENCE (ECL)
- Technique for studying electrogenerated radicals that emit light
- Involves electrochemical generation of light-emitting
excited-state species
- Usually carried out in deoxygenated nonaqueous media
Examples of Species
Ru(bpy)32+
Nitro compounds
Polycyclic hydrocarbons
Luminol
SCANNING ELECTROCHEMICAL
MICROSCOPY (SECM)
- Faradaic currents at a microelectrode tip are measured while the
tip is moved close to the substrate surface immersed in a
solution containing an electroactive species
- The tip currents are a function of the conductivity and chemical
nature of the substrate as well as the tip-substrate distance
Images obtained give information on
- electrochemical activity
- chemical activity
- surface topography
SCANNING ELECTROCHEMICAL
MICROSCOPY (SECM)
- Cannot be used for obtaining atomic resolution
Used to investigate
- Ionic flux through the skin or membranes
- Localized biological activity (biosensors)
- Heterogeneous reaction kinetics
2mnf o2
A
n = overtone number
fo = base resonant frequency of the crystal (prior to mass change)
A = area (cm2)
= shear modulus of quartz (2.95 x 1011 gcm-1s-1)
= density of quartz (2.65 g/cm3)
IMPEDANCE SPECTROSCOPY
- For probing the features of chemically-modified electrodes
- For understanding electrochemical reactions
- For electron transfer kinetics and diffusional
characteristic studies
Impedance
- Complex resistance encountered when a current flows
through a circuit made of combinations of
resistors, capacitors, or inductors
IMPEDANCE SPECTROSCOPY
- Plots of faradaic impedance spectrum is known as Nyquist plot
Consists of
- a semicircle portion at high frequencies
(corresponds to the electron-transfer-limited process)
and
- a straight line portion at low frequencies
(coreesponds to the diffusion-limited process)
IMPEDANCE SPECTROSCOPY
- The impedance spectrum has only the linear portion
for very fast electron transfer processes
- Very slow electron transfer processes are characterized
by a large semicircle region
- Diameter of the semicircle equals the electron
transfer resistance